Arrays of Stereogenic Centers: The Carbery Synthesis of Mycestericin G

Chi-Ming Che of the University of Hong Kong devised
(Chem. Comun.2011, 47, 11204.
)
a manganese catalyst for the enantioselective cis-dihydroxylation of
electron-deficient alkenes such as 1. Christine Greck of Université de
Versailles-St-Quentin effected
(Tetrahedron Lett.2012, 53, 1085.
)
enantioselective alkoxylation of
3, remarkably without β-elimination. Keiji
Maruoka of Kyoto University developed
(J. Am. Chem. Soc.2012, 134, 7516.
)
an organocatalyst for the enantioselective
anti addition of 5 to 6, to give 7.
Barry M. Trost of Stanford University developed
(J. Am. Chem. Soc.2012, 134, 2075.
)
a Mg catalyst for the enantioselective addition of ethyl diazoacetate to
an aldehyde 8, and carried the adduct on to 9.

Professor Maruoka designed
(Angew. Chem. Int. Ed.2012, 51, 1187.
)
for the enantioselective addition of a ketone 10 to the alkynyl
ketone 11, to give 12.
Naoya Kumagai and Masakatsu Shibasaki of the Institute of Microbial Chemistry found
(Org. Lett.2012, 14, 3108.
)
that 14 could be added under very soft conditions to 13 to give
the anti adduct 15. René Peters of the Universität Stuttgart added
(Adv. Synth. Catal.2012, 354, 1443.
)
the azlactone formed in situ to 17 in a conjugate sense to give 18.
Kaïss Aouadi and Jean-Pierre Praly of the Université de Lyon prepared
(Tetrahedron Lett.2012, 53, 2817.
)
the nitrone 19 from the inexpensive (-)-menthone. Dipolar cycloaddition to a range of alkenes
proceeded with substantial diastereocontrol, as illustrated for 20, which gave
the crystalline adduct 21.

David R. Carbery of the University of Bath optimized
(Org. Lett.2012, 14, 756.
)
the diastereoselective Claisen rearrangement of 32 to give the benzyl ester
33. This was carried on via cross metathesis to the immunosuppressant
Mycestericin G (34).